Crystalline transition metal oxy-hydroxide molybdotungstate

ABSTRACT

A hydroprocessing catalyst has been developed. The catalyst is a unique crystalline transition metal oxy-hydroxide molybdotungstate material. The hydroprocessing using the crystalline ammonia transition metal oxy-hydroxide molybdotungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.62/267,870 filed Dec. 15, 2015, the contents of which are herebyincorporated by reference.

FIELD OF THE INVENTION

This invention relates to a new hydroprocessing catalyst. Moreparticularly this invention relates to a unique crystalline transitionmetal oxy-hydroxide molybdotungstate and its use as a hydroprocessingcatalyst. The hydroprocessing may include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking.

BACKGROUND

In order to meet the growing demand for petroleum products there isgreater utilization of sour crudes, which when combined with tighterenvironmental legislation regarding the concentration of nitrogen andsulfur within fuel, leads to accentuated refining problems. The removalof sulfur (hydrodesulfurization—HDS) and nitrogen(hydrodenitrification—HDN) containing compounds from fuel feed stocks istargeted during the hydrotreating steps of refining and is achieved bythe conversion of organic nitrogen and sulfur to ammonia and hydrogensulfide respectively.

Since the late 1940s the use of catalysts containing nickel (Ni) andmolybdenum (Mo) or tungsten (W) have demonstrated up to 80% sulfurremoval. See for example, V. N. Ipatieff, G. S. Monroe, R. E. Schaad,Division of Petroleum Chemistry, 115^(th) Meeting ACS, San Francisco,1949. For several decades now there has been an intense interestdirected towards the development of materials to catalyze the deepdesulfurization, in order to reduce the sulfur concentration to the ppmlevel. Some recent breakthroughs have focused on the development andapplication of more active and stable catalysts targeting the productionof feeds for ultra low sulfur fuels. Several studies have demonstratedimproved HDS and HDN activities through elimination of the support suchas, for example, Al₂O₃. Using bulk unsupported materials provides aroute to increase the active phase loading in the reactor as well asproviding alternative chemistry to target these catalysts.

More recent research in this area has focused on the ultra deepdesulfurization properties achieved by a Ni—Mo/W unsupported‘trimetallic’ material reported in, for example, U.S. Pat. No.6,156,695. The controlled synthesis of a broadly amorphous mixed metaloxide consisting of molybdenum, tungsten and nickel, significantlyoutperformed conventional hydrotreating catalysts. The structuralchemistry of the tri-metallic mixed metal oxide material was likened tothe hydrotalcite family of materials, referring to literature articlesdetailing the synthesis and characterization of a layered nickelmolybdate material, stating that the partial substitution of molybdenumwith tungsten leads to the production of a broadly amorphous phasewhich, upon decomposition by sulfidation, gives rise to superiorhydrotreating activities.

The chemistry of these layered hydrotalcite-like materials was firstreported by H. Pezerat, contribution à l'étude des molybdates hydratesde zinc, cobalt et nickel, C. R. Acad. Sci., 261, 5490, who identified aseries of phases having ideal formulas MMoO₄.H₂O, EHM₂O⁻ (MoO₄)₂.H₂O,and E_(2-x)(H₃O)_(x)M₂O(MoO₄)₂ where E can be NH₄ ⁺, Na⁺ or K⁺ and M canbe Zn²⁺, Co²⁺ or Ni²⁺.

Pezerat assigned the different phases he observed as being Φc, Φy or Φyand determined the crystal structures for Φx and Φy, however owing to acombination of the small crystallite size, limited crystallographiccapabilities and complex nature of the material, there were doubtsraised as to the quality of the structural assessment of the materials.During the mid 1970s, Clearfield et al attempted a more detailedanalysis of the Φx and Φy phases, see examples A. Clearfield, M. J.Sims, R. Gopal, Inorg. Chem., 15, 335; A. Clearfield, R. Gopal, C. H.Saldarriaga-Molina, Inorg. Chem., 16, 628. Single crystal studies on theproduct from a hydrothermal approach allowed confirmation of the Φxstructure, however they failed in their attempts to synthesize Φy andinstead synthesized an alternative phase, Na—Cu(OH)(MoO₄), see A.Clearfield, A. Moini, P. R. Rudolf, Inorg. Chem., 24, 4606.

The structure of Φy was not confirmed until 1996 when by Ying et al.Their investigation into a room temperature chimie douce synthesistechnique in the pursuit of a layered ammonium zinc molybdate led to ametastable aluminum-substituted zincite phase, prepared by thecalcination of Zn/Al layered double hydroxide (Zn₄Al₂(OH)₁₂CO_(3.)zH₂O).See example D. Levin, S. L. Soled, J. Y. Ying, Inorg. Chem., 1996, 35,4191-4197. This material was reacted with a solution of ammoniumheptamolybdate at room temperature to produce a highly crystallinecompound, the structure of which could not be determined throughconventional ab-initio methods. The material was indexed, yieldingcrystallographic parameters which were the same as that of an ammoniumnickel molybdate, reported by Astier, see example M. P. Astier, G. Dji,S. Teichner, J. Ann. Chim. (Paris), 1987, 12, 337, a material belongingto a family of ammonium-amine-nickel-molybdenum oxides closely relatedto Pezerat's materials. Astier did not publish any detailed structuraldata on this family of materials, leading to Ying et al reproducing thematerial to be analyzed by high resolution powder diffraction in orderto elucidate the structure. Ying et al named this class of materials‘layered transition-metal molybdates’ or LTMs.

SUMMARY OF THE INVENTION

A unique crystalline transition metal oxy-hydroxide molybdotungstatematerial has been produced and optionally sulfided, to yield an activehydroprocessing catalyst. The crystalline transition metal oxy-hydroxidemolybdotungstate material has a unique x-ray powder diffraction patternshowing strong peaks at 9.65, 7.3 and 5.17 Å. The crystalline transitionmetal oxy-hydroxide molybdotungstate material has the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)—where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ varies from 0.01 to 0.4, or from0.01 to 0.25; where the sum of (x+y) must be ≤1.501, or ≤1.2 ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A:

TABLE A d(Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.91 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

Another embodiment involves a method of making a crystalline transitionmetal oxy-hydroxide molybdotungstate material having the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)—where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ varies from 0.01 to 0.4, or from0.01 to 0.25; where the sum of (x+y) must be ≤1.501, or ≤1.2 ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A:

TABLE A d(Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.91 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

the method comprising forming a reaction mixture containing NH₃, H₂O,and sources of M, W, and Mo; adjusting the pH of the reaction mixture toa pH of from about 8.5 to about 10; reacting the mixture together atelevated temperature with an autogenous pressure and then recovering thecrystalline transition metal oxy-hydroxide molybdotungstate material.The reacting may be conducted at a temperature of from 70° C. to about200° C. for a period of time from about 30 minutes to 14 days.

Yet another embodiment involves a conversion process comprisingcontacting a feed with a catalyst at conversion conditions to give atleast one product, the catalyst comprising: a crystalline transitionmetal oxy-hydroxide molybdotungstate material having the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)—where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ varies from 0.01 to 0.4, or from0.01 to 0.25; where the sum of (x+y) must be ≤1.501, or ≤1.2 ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A:

TABLE A d(Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.91 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

Additional features and advantages of the invention will be apparentfrom the description of the invention, the FIGURE and claims providedherein.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is the x-ray powder diffraction pattern of a crystallinetransition metal oxy-hydroxide molybdotungstate prepared by boilingcrystallization as described in Examples 1 to 3.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a crystalline transition metaloxy-hydroxide molybdotungstate material and a process for preparing thematerial. The material has the designation UPM-9. The crystallinetransition metal oxy-hydroxide molybdotungstate material has anempirical formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)—where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ varies from 0.01 to 0.4, or from0.01 to 0.25; where the sum of (x+y) must be ≤1.501, or ≤1.2 ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y.

The crystalline composition of the invention is characterized by havingan extended network of M-O-M, where M represents a metal, or combinationof metals listed above. The structural units repeat itself into at leasttwo adjacent unit cells without termination of the bonding. Thecomposition can have a one-dimensional network, such as, for example,linear chains.

The crystalline transition metal oxy-hydroxide molybdotungstatecomposition having an x-ray powder diffraction pattern showing peaks atthe d-spacings listed in Table A.

TABLE A d(Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.91 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

The crystalline transition metal oxy-hydroxide molybdotungstatecomposition of the invention having the x-ray powder diffraction patternshown in the FIGURE.

The crystalline transition metal oxy-hydroxide molybdotungstatecomposition is prepared by solvothermal crystallization of a reactionmixture typically prepared by mixing reactive sources of molybdenum andtungsten with a solvent as well as a source of ammonia. Specificexamples of the molybdenum source which may be utilized in thisinvention include but are not limited to molybdenum trioxide, ammoniumdimolybdate, ammonium thiomolybdate, and ammonium heptamolybdate.Specific examples of the tungsten source which may be utilized in thisinvention include but are not limited to tungsten trioxide, ammoniumditungstate, ammonium thiotungstate, and ammonium metatungstate. Sourcesof other metals “M” include but are not limited to the respectivehalide, acetate, nitrate, carbonate, thiols and hydroxide salts.Specific examples include nickel chloride, cobalt chloride, nickelbromide, cobalt bromide, magnesium chloride, nickel nitrate, cobaltnitrate, iron nitrate, manganese nitrate, zinc nitrate, nickel acetate,cobalt acetate, iron acetate, nickel carbonate, cobalt carbonate, zinccarbonate, nickel hydroxide and cobalt hydroxide.

The source of ammonia may include but is not limited to ammoniumhydroxide, ammonium carbonate, ammonium bicarbonate, ammonium chloride,ammonium fluoride or a combination thereof.

Generally, the solvothermal process used to prepare the composition ofthis invention involves forming a reaction mixture wherein all of thecomponents, such as for example, Ni, Mo, NH₃ and H₂O are mixed insolution together. By way of one specific example, a reaction mixturemay be formed which in terms of molar ratios of the oxides is expressedby the formula:AMO_(X):BMOO_(Y):CWO_(Z):D(NH₃): H₂Owhere ‘M’ is selected from the group consisting of iron, cobalt, nickel,manganese, copper, zinc and mixtures thereof; ‘A’ represents the molarratio of ‘M’ and varies from 0.1 to 3 or from 0.5 to 2 or from 0.75 to1.25; ‘x’ is a number which satisfies the valency of ‘M’; ‘B’ representsthe molar ratio of ‘Mo’ and varies from 0.1 to 3 or from 0.5 to 2 orfrom 0.75 to 1.25; ‘y’ is a number satisfies the valency of ‘Mo’; ‘B’represents the molar ratio of ‘W’ and varies from 0.01 to 1 or from 0.05to 0.8 or from 0.1 to 0.6; ‘D’ represents the molar ratio of NH₃ andvaries from 0.01 to 50 or from 0.1 to 40 or from 1 to 30; the molarratio of H₂O and varies from 10 to 1000 or from 50 to 500 or from 90 to300.

The pH of the mixture is adjusted to a value ranging from about 7.5 toabout 11, or from about 8.5 to about 10. The pH of the mixture can becontrolled through the addition of a base such as NH₄OH, quaternaryammonium hydroxides, amines, and the like.

Once the reaction mixture is formed, the reaction mixture is reacted attemperatures ranging from about 70° C. to about 230° C. for a period oftime ranging from 30 minutes to around 14 days. In one embodiment thetemperate range for the reaction is from about 110° C. to about 120° C.and in another embodiment the temperature is in the range of from about150° C. to about 180° C. In one embodiment, the reaction time is fromabout 4 to about 6 hours, and in another embodiment the reaction time isfrom about 7 to about 10 days. The reaction is carried out underatmospheric pressure or in a sealed vessel under autogenous pressure. Inone embodiment the synthesis may be conducted in an open vessel underreflux conditions. The crystalline transition metal oxy-hydroxidemolybdotungstate compositions are recovered as the reaction product. Thecrystalline transition metal oxy-hydroxide molybdotungstate compositionsare further characterized by their x-ray powder diffraction pattern asshown in Table A above and the FIGURE.

Once formed, the crystalline transition metal oxy-hydroxidemolybdotungstate composition may have a binder incorporated, where theselection of binder includes but is not limited to, anionic and cationicclays such as hydrotalcites, pyroaurite-sjogrenite-hydrotalcites,montmorillonite and related clays, kaolin, sepiolites, silicas, aluminasuch as (pseudo) boehomite, gibbsite, flash calcined gibbsite,eta-alumina, zicronica, titania, alumina coated titania, silica-alumina,silica coated alumina, alumina coated silicas and mixtures thereof, orother materials generally known as particle binders in order to maintainparticle integrity. These binders may be applied with or withoutpeptization. The binder may be added to the bulk crystalline transitionmetal oxy-hydroxide molybdotungstate composition, and the amount ofbinder may range from about 1 to about 30 wt % of the finished catalystsor from about 5 to about 26 wt % of the finished catalyst. The bindermay be chemically bound to the crystalline transition metaloxy-hydroxide molybdotungstate composition, or may be present in aphysical mixture with the crystalline transition metal oxy-hydroxidemolybdotungstate composition.

The crystalline transition metal oxy-hydroxide molybdotungstatecomposition, with or without an incorporated binder can then be sulfidedor pre-sulfided under a variety of sulfidation conditions, these includethrough contact of the crystalline transition metal oxy-hydroxidemolybdotungstate composition with a sulfur containing feed as well asthe use of a gaseous mixture of H₂S/H₂. The sulfidation of thecrystalline transition metal oxy-hydroxide molybdotungstate compositionis performed at elevated temperatures, typically ranging from 50 to 600°C., or from 150 to 500° C., or from 250 to 450° C.

The unsupported crystalline transition metal oxy-hydroxidemolybdotungstate material of this invention can be used as a catalyst orcatalyst support in various hydrocarbon conversion processes.Hydroprocessing processes is one class of hydrocarbon conversionprocesses in which the crystalline transition metal oxy-hydroxidemolybdate material is useful as a catalyst. Examples of specifichydroprocessing processes are well known in the art and includehydrodenitrification, hydrodesulfurization, hydrodemetallation,hydrodesilication, hydrodearomatization, hydroisomerization,hydrotreating, hydrofining, and hydrocracking

The operating conditions of the hydroprocessing processes listed abovetypically include reaction pressures from about 2.5 MPa to about 17.2MPa, or in the range of about 5.5 to about 17.2 MPa, with reactiontemperatures in the range of about 245° C. to about 440° C., or in therange of about 285° C. to about 425° C. Time with which the feed is incontact with the active catalyst, referred to as liquid hour spacevelocities (LHSV), should be in the range of about 0.1 h⁻¹ to about 10h⁻¹, or about 2.0 h⁻¹ to about 8.0 h⁻¹. Specific subsets of these rangesmay be employed depending upon the feedstock being used. For examplewhen hydrotreating a typical diesel feedstock, operating conditions mayinclude from about 3.5 MPa to about 8.6 MPa, from about 315° C. to about410° C., from about 0.25/h to about 5/h, and from about 84 Nm³ H₂/m³ toabout 850 Nm³ H₂/m³ feed. Other feedstocks may include gasoline,naphtha, kerosene, gas oils, distillates, and reformate.

Examples are provided below so that the invention may be described morecompletely. These examples are only by way of illustration and shouldnot be interpreted as a limitation of the broad scope of the invention,which is set forth in the appended claims.

Patterns presented in the following examples were obtained usingstandard x-ray powder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 mA. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Powder samples were pressed flat into a plateand continuously scanned from 3° and 70° (2θ). Interplanar spacings (d)in Angstrom units were obtained from the position of the diffractionpeaks expressed as θ, where θ is the Bragg angle as observed fromdigitized data. Intensities were determined from the integrated area ofdiffraction peaks after subtracting background, “Io” being the intensityof the strongest line or peak, and “I” being the intensity of each ofthe other peaks. As will be understood by those skilled in the art thedetermination of the parameter 2θis subject to both human and mechanicalerror, which in combination can impose an uncertainty of about ±0.4° oneach reported value of 2θ. This uncertainty is also translated to thereported values of the d-spacings, which are calculated from the2θvalues. In some of the x-ray powder diffraction patterns reported, therelative intensities of the d-spacings are indicated by the notationsvs, s, m, and w, which represent very strong, strong, medium, and weak,respectively. In terms of 100(I/I₀), the above designations are definedas:

-   -   w=greater than 0 to 15, m=15-60, s=60-80 and vs=80-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray powder diffraction pattern of the sample is free of linesattributable to crystalline impurities, not that there are no amorphousmaterials present. As will be understood to those skilled in the art, itis possible for different poorly crystalline materials to yield a peaksat the same position. If a material is composed of multiple poorlycrystalline materials, then the peak positions observed individually foreach poorly crystalline materials would be observed in the resultingsummed diffraction pattern. Likewise it is possible to have some peaksappear at the same positions within different, single phase, crystallinematerials, which may be simply a reflection of a similar distance withinthe materials and not that the materials possess the same structure.

EXAMPLE 1

In a 2 liter flask, 125.71 g of nickel nitrate hexahydrate (0.43 molesof Ni), 23.2 g of molybdenum trioxide (0.16 moles of Mo) and 77 g ofammonium metatungstate (0.31 moles of W) were dissolved in 1200 ml ofwater. The pH of the solution was increased to approximately 9 usingconcentrated NH₄OH (approximately 300 ml). At this point the solutionwas transferred to a 2-liter stainless steel autoclave, the heat wasramped to 180° C. over a period of 2hours and held at 180° C. for 24hours, after which time the autoclave was cooled to room temperature,filtered, washed with 90 ml of about 90° C. water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectrashown in the FIGURE.

EXAMPLE 2

In a 2 liter flask, 104.76 g of nickel nitrate hexahydrate (0.36 molesof Ni), 126.96 g of ammonium heptamolybdate (0.72 moles of Mo) and 53.28g of ammonium metatungstate (0.21 moles of W) were dissolved in 1008 mlof water. The pH of the solution was increased to approximately 9 usingconcentrated NH₄OH (approximately 100 ml). At this point the solutionwas transferred to a 2-liter stainless steel autoclave, the heat wasramped to 180° C. over a period of 2 hours and held at 180° C. for 24hours, after which time the autoclave was cooled to room temperature,filtered, washed with 90 ml of about 90° C. water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectrashown in the FIGURE.

EXAMPLE 3

In a 2 liter flask, 104.76 g of nickel nitrate hexahydrate (0.36 molesof Ni), 95.22 g of ammonium heptamolybdate (0.54 moles of Mo) and 53.28g of ammonium metatungstate (0.21 moles of W) were dissolved in 1008 mlof water. The pH of the solution was increased to approximately 9 usingconcentrated NH₄OH (approximately 100 ml). At this point the solutionwas transferred to a 2-liter stainless steel autoclave, the heat wasramped to 180° C. over a period of 2 hours and held at 150° C. for 7days, after which time the autoclave was cooled to room temperature,filtered, washed with 90 ml of about 90° C. water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectrashown in the FIGURE.

Embodiments

Embodiment 1 is a crystalline transition metal oxy-hydroxidemolybdotungstate material having the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)—where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ varies from 0.01 to 0.4, or from0.01 to 0.25; where the sum of (x+y) must be ≤1.501, or ≤1.2 ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A:

TABLE A d(Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.91 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

The crystalline transition metal oxy-hydroxide molybdotungstate materialof embodiment 1 wherein the crystalline transition metal oxy-hydroxidemolybdotungstate material is present in a mixture with at least onebinder and wherein the mixture comprises up to 25 wt % binder.

The crystalline transition metal oxy-hydroxide molybdotungstate materialof embodiment 1 wherein the crystalline transition metal oxy-hydroxidemolybdotungstate material is present in a mixture with at least onebinder and wherein the mixture comprises up to 25 wt % binder andwherein the binder is selected from the group consisting of silicas,aluminas, and silica-aluminas.

The crystalline transition metal oxy-hydroxide molybdotungstate materialof embodiment 1 wherein the crystalline transition metal oxy-hydroxidemolybdotungstate material is sulfided.

Embodiment 2is a method of making a crystalline transition metaloxy-hydroxide molybdotungstate material having the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)—where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ varies from 0.01 to 0.4, or from0.01 to 0.25; where the sum of (x+y) must be ≤1.501, or ≤1.2 ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A:

TABLE A d(Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.91 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

the method comprising: (a) forming a reaction mixture containing NH₃,H₂O, and sources of M, W, and Mo; (b) adjusting the pH of the reactionmixture to a pH of from about 8.5 to about 10; (c) reacting the reactionmixture between about 100° C. and about 220° C. in an autogenousenvironment, and (d) recovering the crystalline transition metaloxy-hydroxide molybdotungstate material.

The method of embodiment 2 wherein the reacting is conducted at atemperature of from 100° C. to about 200° C. for a period of time fromabout 30 minutes to 14 days.

The method of embodiment 2 wherein the recovering is by filtration orcentrifugation.

The method of embodiment 2 further comprising adding a binder to therecovered crystalline transition metal oxy-hydroxide molybdotungstatematerial.

The method of embodiment 2 further comprising adding a binder to therecovered crystalline transition metal oxy-hydroxide molybdotungstatematerial wherein the binder is selected from the group consisting ofaluminas, silicas, and alumina-silicas.

The method of embodiment 2 further comprising sulfiding the recoveredcrystalline transition metal oxy-hydroxide molybdotungstate material.

Embodiment 3 is a conversion process comprising contacting a feed with acatalyst at conversion conditions to give at least one product, thecatalyst comprising: a crystalline transition metal oxy-hydroxidemolybdotungstate material having the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)—where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ varies from 0.01 to 0.4, or from0.01 to 0.25; where the sum of (x+y) must be ≤1.501, or ≤1.2 ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A:

TABLE A d(Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.91 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

The process of embodiment 3 wherein the conversion process ishydroprocessing.

The process of embodiment 3 wherein the conversion process is selectedfrom the group consisting of hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

The process of embodiment 3 wherein the crystalline transition metaloxy-hydroxide molybdotungstate material is present in a mixture with atleast one binder and wherein the mixture comprises up to 25 wt % binder.

The process of embodiment 3 wherein the crystalline transition metaloxy-hydroxide molybdotungstate material is sulfided.

The invention claimed is:
 1. A crystalline transition metaloxy-hydroxide molybdotungstate material having the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)— where “a” varies from 0.1 to 10,‘M’ is a metal selected from Mg, Mn, Fe, Co, Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5; ‘y’varies from 0.01 to 0.4; where the sum of (x+y) must be ≤1.501; ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A: TABLE A d(Å) I/I₀ % 10.0-9.53 m7.72-7.76 s 7.49-7.25 m 5.27-5.12 m  5.1-5.04 m 4.92-4.87 w 3.97-3.91 m3.69-3.64 s 3.52-3.48 m 3.35-3.32 m 3.31-3.29 m 3.12-3.09 w   3-2.97 m2.76-2.73  m.


2. The crystalline transition metal oxy-hydroxide molybdotungstatematerial of claim 1 wherein the crystalline transition metaloxy-hydroxide molybdotungstate material is present in a mixture with atleast one binder and wherein the mixture comprises up to 25 wt % binder.3. The crystalline transition metal oxy-hydroxide molybdotungstatematerial of claim 2 wherein the binder is selected from the groupconsisting of silicas, aluminas, and silica-aluminas.
 4. The crystallinetransition metal oxy-hydroxide molybdotungstate material of claim 1wherein the crystalline transition metal oxy-hydroxide molybdotungstatematerial is sulfided.
 5. A method of making a crystalline transitionmetal oxy-hydroxide molybdotungstate material having the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)— where “a” varies from 0.1 to 10,‘M’ is a metal selected from Mg, Mn, Fe, Co, Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5; ‘y’varies from 0.01 to 0.4; where the sum of (x+y) must be ≤1.501; ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A: TABLE A d(Å) I/I₀ % 10.0-9.53 m7.72-7.76 s 7.49-7.25 m 5.27-5.12 m  5.1-5.04 m 4.92-4.87 w 3.97-3.91 m3.69-3.64 s 3.52-3.48 m 3.35-3.32 m 3.31-3.29 m 3.12-3.09 w   3-2.97 m2.76-2.73 m

the method comprising: (a) forming a reaction mixture containing NH₃,H₂O, and sources of M, W, and Mo; (b) adjusting the pH of the reactionmixture to a pH of from about 8.5 to about 10; (c) reacting the reactionmixture between about 100° C. and about 220° C. in an autogenousenvironment; and (d) recovering the crystalline transition metaloxy-hydroxide molybdotungstate material.
 6. The method of claim 5wherein the reacting is conducted at a temperature of from 10° C. toabout 200° C. for a period of time from about 30 minutes to 14 days. 7.The method of claim 5 wherein the recovering is by filtration orcentrifugation.
 8. The method of claim 5 further comprising adding abinder to the recovered crystalline transition metal oxy-hydroxidemolybdotungstate material.
 9. The method of claim 8 wherein the binderis selected from the group consisting of aluminas, silicas, andalumina-silicas.
 10. The method of claim 5 further comprising sulfidingthe recovered crystalline transition metal oxy-hydroxidemolybdotungstate material.
 11. A hydroprocessing process comprisingcontacting a feed with a catalyst at hydroprocessing conditions to giveat least one product, the catalyst comprising: a crystalline transitionmetal oxy-hydroxide molybdotungstate material having the formula:—(NH₄)_(a)M(OH)_(b)Mo_(x)W_(y)O_(z)— where “a” varies from 0.1 to 10,‘M’ is a metal selected from Mg, Mn, Fe, Co, Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5; ‘y’varies from 0.01 to 0.4; where the sum of (x+y) must be ≤1.501; ‘z’ is anumber which satisfies the sum of the valency of a, M, b, x and y; thematerial having a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A: TABLE A d(Å) I/I₀ % 10.0-9.53 m7.72-7.76 s 7.49-7.25 m 5.27-5.12 m  5.1-5.04 m 4.92-4.87 w 3.97-3.91 m3.69-3.64 s 3.52-3.48 m 3.35-3.32 m 3.31-3.29 m 3.12-3.09 w   3-2.97 m2.76-2.73  m.


12. The process of claim 11 wherein the hydroprocessing process isselected from the group consisting of hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking.
 13. The process of claim 11 wherein the crystallinetransition metal oxy-hydroxide molybdotungstate material is present in amixture with at least one binder and wherein the mixture comprises up to25 wt % binder.
 14. The process of claim 11 wherein the crystallinetransition metal oxy-hydroxide molybdotungstate material is sulfided.